Herbicidal allophanimidates

ABSTRACT

Herbicidal allophanimidic acid esters of the formula:   WHERE R1, R2, R4 and R5 are selected from hydrogen and certain organic radicals, at least one of them being an organic radical; R3 is selected from hydrogen and certain organic radicals; R6 is selected from certain organic radicals; and X1, X2, and X3 are selected from oxygen and sulfur; AND SALTS OF THE ABOVE COMPOUNDS IN WHICH R3 is hydrogen. Preparation of the compounds by carbamoylation of   OR BY REACTION OF AMMONIA OR AN AMINE WITH   WHERE Y is -SCH3, -Cl,   An exemplary compound: methyl N-dimethylcarbamoyl-4-tertbutylthioallophanimidate.

Umted States Patent 1191 1111 3,879,190

Fuchs 1451 Apr. 22, 1975 1 HERBlClDAL ALLOPHANlMlDATES [76] Inventor:Julius Jakob Fuchs, 1 104 Greenway 1571 ABSTRACT Rd. Wilmington. Del.19803 Herbicidal allophanimidic acid esters of the formula:

7 [2-] Flled. July 3, 1972 1 1 3 5? M 21 Appl. No.: 268,768 N g-N=C-I--C-N Related U.S. Application Data 1 l [631 Continuation-impartof Ser. No. 256.254. May 24. 2 2'R6 5 1972, abandoned. which is acontinuation-in-part of Scr. No. 181.203. Sept. 16. 1971. abandoned.here R R R and R are selected from hydrogen and 1521 us. 01. 71/98;71/88; 71 /94; Organic radicals least one of them 71/95; 71/99; 71 119;71/120; 260/239 F; F an organ? 260/239 BF; 260/2471; 260/2472 A; R;, 1sse1ected from hydrogen and certam organlc 260/2472 13-. 260/2475 R;260/243.58; Ftdlcals;

260093.62; 260/29363; 260/293'85; R. 1s selected from certaln orgamcrad1ca1s; and

260/291; 260/309; 260/3268}; X,, X and X are selected from oxygen andsulfur; 2 053 3; 2 032 2 0 R; and salts of the above compounds in whichR, is hy- 260/470; 260/471 R; 260/481 R; 260/482 R: dmgen- 260/455 A;260/543 A; 260/544 C; 260/566 Preparation of the compounds bycarbamoylation of D 51 1111.01 A0ln 9/12 1 5 (58] Field of Search 71/98.99,120,119:

260/453 R, 552 R. 564 E 3 R X -R (56] References Cited 2 2 6 UNITEDSTATES PATENTS or by reaction of ammonia or an amine with 1,667,0534/1928 Schottc 260/552 R R 2.780.535 2/1957 Snyder 71/98 1 $3 {13.439.018 4/1969 Brookcs ct a1 71/118 N C C N-C Y 3.488.355 1/1970 Levy260/453 R 3,597,444 8/1971 Klayman et a1 260/3097 2 2 6 FOREIGN PATENTSOR APPLICATIONS "16.958 1/1966 Japan 71/99 where Y 16470 11/1968 Japan71/99 OTHER PUBLICATIONS Najer et a1., "Action of Oxalyl Chloride onN,N- dialkylaceas. etc." (1959) CA 54 p. 9759 (1960). Sonn. Biuret andTriuret from Urea" (1942) CA 37 p. 6281 (1943).

Primary E.\aminerG1ennon H. Hollrah An exemplary compound: methylN-dimethylcarbamoy1-4-tert-buty1thioa11ophanimidate.

4 Claims, N0 Drawings HERBICIDAL ALLOPHANIMIDATES BACKGROUND OF THEINVENTION US. Pat. No. 3.530.220. issued Sept. 22. 1970. to James B.Buchanan. discloses a class of l-carbamoyl- N-(substitutedcarbamoyloxy)thioformimidates of the general formula where the Rsrepresent hydrogen or certain organic radicals and R and R" representcertain organic radicals. The compounds are insecticides. acaricides.and nematocides. The patent discloses preparation of the compounds fromintermediate l-carbamoyl-N- hydroxythioformimidates of the generalformula R S-R' The present invention resulted from efforts to discovernew biologically active compounds which could be prepared from theseintermediates.

SUMMARY OF THE INVENTION This invention is a class of novel herbicidallyactive compounds of the formula:

wherein:

R R R and R are each independently selected from the group consisting ofhydrogen; alkyl of I through 8 carbon atoms; alkenyl of 3 through 4carbon atoms; cycloalkyl of 3 through 8 carbon atoms; cycloalkenyl of 5through 8 carbon atoms; cyclmtlkylalkyl of4 through 10 carbon atoms;bicycloalkyl of 7 through 10 carbon atoms; arylalkyl of 5 through 9carbon atoms: alkynyl of 3 through 4 carbon atoms; methoxy; phenyl; theabove alkyl and alkenyl groups substituted with I through 3 chlorines.bromine. iodine. I through 7 fluorines. methoxy. ethoxy. methylthio.ethylthio. cyano. methoxycarbonyl. ethoxycarlmnyl. or acetyl; the abovecycloalkyl and bicycloalkyl groups substituted with I through 3chlorines. bromine. I or 2 methyls. or alkyl of 2 through 4 carbonatoms; phenyl substituted with l or 2 chlorines. l or 2 bromines.fluorine. nitro. cyano. alkyl of I through 4 carbon atoms. methoxy. ortrifluoromethyl; and the above arylalkyl groups substituted with lchlorine or I methyl;

R and R when taken together and R and R when taken together are. --(CH--O(CH or --(CH:),,- where n is 2 through 6;

R is hydrogen; alkyl of I through 4 carbon atoms: alkynyl of 3 through 4carbon atoms; or alkenyl of 3 through 4 carbon atoms;

R. is alkyl of I through 8 carbon atoms; cycloalkyl of 5 through 8carbon atoms; alkenyl of 3 through 8 carbon atoms; phenyl; or benzyl;and

X X and X are each independently selected from oxygen and sulfur:

provided that:

a. at least one of R R R and R is other than hydrogen:

b. no more than one of R R R and R is phenyl.

substituted phenyl; arylalkyl or substituted arylalkyl;

c. the total number of carbon atoms in R and R does not exceed 10:

d. the total number of carbon atoms in R and R;

does not exceed 10;

e. R and R- are not both methoxy;

f. R. and R are not both methoxy;

g. when one of R,. R R and R is methoxycarbonylmethyl orethoxycarbonylmethyl and R is hydrogen then only one of the other R R Rand R can be other than hydrogen;

h. when R is normal alkyl of 3 through 8 carbon atoms. cycloalkyl of 6through 8 carbon atoms and benzyl. and R is hydrogen. and one of R,. R Rand R is phenyl. then only one of the other R R R and R can be otherthan hydrogen: and

i. when one of R R R and R is 2.5-dichlorophenyl and R is hydrogen. thenonly one of the other R,. R R and R can be other than hydrogen;

and salts of the above compounds in which R is hydrogen.

The invention also includes herbicidal compositions containing thecompounds as active ingredient. methods of controlling undesiredvegetation by applying the compounds. methods of preparing thecompounds. and certain intermediates (Compounds of formulae II. III andV below) useful in preparing the compounds.

DESCRIPTION OF THE INVENTION Preferred Compounds Preferred because ofhigher herbicidal activity and ease of synthesis are those compounds offormula I where R, is hydrogen. alkyl of I through 6 carbon atoms. or

alkenyl of 3 through 4 carbon atoms:

R is alkyl of I through 4 carbon atoms or alkenyl of 3 through 4 carbonatoms. provided that the total number of carbon atoms in R and R doesnot exceed 8;

R is hydrogen;

R is alkyl of I through 6 carbon atoms; alkenyl of 3 through 4 carbonatoms or cycloalkyl of 5 through 6 carbon atoms;

R;, is hydrogen. alkyl of I through 6 carbon atoms. cycloalkyl of 5through 6 carbon atoms. benzyl. or alkenyl of 3 through 4 carbon atoms:

R is methyl. ethyl. isopropyl or allyl;

X and X; are oxygen; and

X is oxygen or sulfur.

Most preferred because of their higher activity are those compounds offormula l where R, is hydrogen or methyl:

R is alkyl of 1 through 4 carbon atoms.

R; is hydrogen:

R is alkyl of I through 4 carbon atoms. allyl or cycloalkyl of 5 through6 carbon atoms:

R,-, is hydrogen:

R is methyl:

X and X;, are oxygen: and

X is sulfur.

The compounds of formula I where R4 is phenyl or substituted phenyl arepreferred for some uses as they have exhibited selective herbicidalactivity in crops such as corn and cotton.

Preferred compounds of formula I include:

methyl N-n-butylcarbamyl-4n-butylthioallophanimidate Synthesis of theFinal Products Compounds of formula I can be prepared by either of thefollowing two reactions:

and R through R and X through X are as hereinbefore defined. exceptthat: in the isocyanates and isothiocyanates (R NCX3). R is not methoxy:in the carbamoyl and thiocarbamoyl chlorides (R R,-,NCX -,Cl). R and Rare not both H: and

X; in R NCX is not sulfur when X in the compound of formula II issulfur.

Carbamylation reaction A is carried out in an inert organic solvent suchas methylene chloride. acetone. ethyl acetate. benzene. CCI... CH Cl orpetroleum ether. at a temperature in the range of about to 100C. Atemperature in the range of about 0 to 100C is usually used. and atemperature in the range of about 20 to C is usually preferred. Theoptimum temperature in a given instance. of course. will depend upon thereactivity of the starting materials involved. When the carbamylatingagent is HNCX the reaction is carried out in a nonpolar solvent. and thereactant is conveniently generated in situ by reaction of an alkalimetal cyanate or thiocyanate (e.g. NaCNO or NaNCS) and an acid (e.g. HClor CF COOH). When the carbamylating agent is R R NCX CL the reaction iscarried out in a nonpolar solvent in presence of an acid acceptor suchas pyridine or triethylamine.

Reaction B is also carried out in an inert organic solvent. such asmethanol, dimethylformamide (DMF). dimethylsulfoxide (DMSO). or acetone.Temperatures in the range of about -l0 to C are suitable. A temperaturein the range of about 050C is usually used. and ambient temperature ispreferred.

Both reactions A and B can be carried out at reduced or elevatedpressures. For example. pressures in the range of ().l to 3 atmospherescan be used. but atmospheric pressure is suitable in most cases. and ispreferred.

The salts of those compounds of formula l where R is H are prepared asfollows:

where M 1s a cation such as Li, Na". K*, Cs.

(Ca/2)". (Mg/2)" (NH or quaternary ammonium.

The reaction is run in water with optional water miscible solvents.

R1 X RANCX N-CN=CNHR or I 5 R X2"R6 RAR NCX CJ.

(B) R y R x l ti i n N-C-N=C-N-- R R NH I I C Y 5 R2 X2R6 III where Y is-SCH,,. Cl.

or JION 3 Alternatively. a salt exchange reaction can be used. as forexample solution of the sodium salt in water followed by addition of asolution of calcium chloride to precipitate the less soluble calciumsalt.

Synthesis of lntermediates Intermediates of formula ll can be preparedin various ways. as illustrated by the following processes: Process IAll compounds of formula ll wherein X is oxygen can be made by thefollowing two step process:

Step 1 R2. X2-R6 R2 Step 2 V l- NH R IT (X :O)

Step1 The Beckmann rearrangement of the formhydroxais preferred sincethe reaction products often crystallize out and can be isolated byfiltration. or can be extracted with a water immiscible solvent.Reaction temperatures of from 0 to 40C can be employed. However. highertemperatures should be avoided since mercaptan can be split off from thestarting material: thus preferred temperatures are in the range ofl3()C.

R n S0012 N-C-N=C-Cl Process 2 The compounds of formula II wherein matesand thioformhydroxamates of formula IV to the formimidoyl andthioformimidoyl chlorides of formula X is oxygen. V can be carried outwith PCl POCL, or SOCl in any X: is sulfur. inert solvent which willdissolve the reaction product. R, and R- are both other than hydrogen.and R is R. such as benzene. toluene. CCI CHCL, or CH Cl where IMethylene chloride and thionyl chloride are preferred R is methyl.ethyl. propyl. isopropyl. n-butyl. allyl,or because of gaseous reactionproducts being formed benzyl, from the acid chloride. and because of thehigh volatilcan also be made by the following two-step process:

Step 1 O R O S l\ n It /NCN=C:S -l- NH R NC-NH-C-NHF5 a R 2 v1 VII Step2 VII R 1 --9 II (X =O, X =S,

R =R R fH, R 9H) ity of the solvent. The temperature of the reaction isp 1 not critical. Experience has shown that a reaction tem- Th6 ynthesisOf Cllrbumoyllsothlocyanates of forperature below room temperature givesincreased mull VI and Comerslon 10 the Correspondmg yields of theformimidoyl chloride; thus the preferred thiobiurets f formul V" c n ecarried out as derange is ()-20C. The thioformhydroxamates of forscribedy P O 11nd E. e ll li m J- Orgmula lV (X S) are prepared as described inUS. Pat. Chem- 2073 No. 3.560550. The formhydroxamates of formula IV p 2(X =O) are prepared by reacting one mole of a The alkylation ofthiobiurets of formula V" can be l-carbamoylformhydrosamyl chloride withtwo equivaperformed analogous to a method given by M. R. lents of analkoxide of the formula R ONa in an inert hflL ru S n Agr. Biol. Chem.32, N0. 6. 71 l (1968) solvent at a temperature in the range of 7() tol()C. for alkylation of o-iodo-2-thio-3-benzylquinazolin-3.4- Step 2(lH.3l-l)-dione to 6-iodo-2-isopropylthio-3-benzyl-4- The reaction ofthe formimidoyl and thioformimidoyl (3H)-quinazolone. chlorides offormula V with ammonia or amines can be M Process 3 carried out inwater. lower alcohols. benzene. CH. Cl or other solvents. which do notreact with ammonia or amines under the reaction conditions employed.Water Compounds of formula ll wherein X is oxygen. and R, and R are bothother than hydrogen. can also be made by the following two-step process:

p 1 R1 c1 n vi 2Cl 9 N-C-N=C R2 Cl VIII Step 2 R X Na NH R VIII V .e II(X =0) Step I Step I is carried out in water or an inert organic sol-The chlorinated of isothiocyanates to imidoyldichlorides of formula VIIIis known in the art and can be performed analogous to a method given byE. Kuehle et al.. Angew. Chem. 79. 663 (1967). who teaches convertingdichloroacetylisothiocyanate with chlorine todichloroacetylcarbonimidoyl dichloride.

Step 2 The stepwise replacement of the two chlorine atoms is bestaccomplished in alcohols as solvents. in which all reactants aresoluble. The reaction temperature must be low in the first step. sinceimidoyldichlorides react above room temperature with alcohols tocarbamates. Preferred temperatures in the first step are 20 to +l()C.Since the second Cl-atom is less reactive than the first. slightlyhigher reaction temperatures are possible with a preferred range of -l0to 30C. Process 4 All compounds of formula ll wherein R- is H. exceptthose wherein R is methoxy. can be made as follows:

This reaction can be conducted as described in German Patent No.1.962.797.

Process 5 The compounds of formula ll wherein R and R are H. X isoxygen. X is sulfur. R is hydrogen. and R is R where R; is as definedabove. can be made as follows:

vent in presence of a base such as sodium hydroxide or l5 tricthylamine.Temperatures in the range of ()50C and atmospheric pressure aresatisfactory.

Step 2 is carried out in an inert organic solvent such as methanol. DMF.DMSO. or acetone at a temperature in the range of about l() to 100C;ambient temperature is preferred.

intermediates of formula lll can be prepared by the following processesProcess 7 All compounds of formula III wherein R and R are H and Y isSCH or Cl can be prepared as follows:

Step l is the same as step I of Process 6 and is carried out under thesame conditions.

Step 2 is carried out in an inert non-polar solvent such as acetonitrileor methylene chloride. A reaction temperature in the range of about()100C and atmo- This reaction is performed analogous to step 2 ofProcess 2. The starting material (X) can be prepared according to US.Pat. No. 2.37l.l l3 Process 6 spheric pressure are satisfactory. Ifdesired a catalyst such as triethylamine or dibutyltin dilaurate can beused. When R is H. the reactant (HNCX,) is conveniently generated insitu by reaction of an alkali metal V All compounds of formula ll can bemade as follows: isocyanate or thiocyanate and an acid. Step 1 X1 X X126 u u I IX ClCSQH CH3SC-N=C-NHR Step 2 1 XI -1m II Process 8 pound (B)covers a longer chain. all intermediates ex All compounds of formula IIIcan be prepared as folisting in either form (A) or (B) are hereaftercalled allows: lophanimidates.

for example: X3 5 CH 0 S-CH -CH=CH II III n i 2 2 N- C-N=C-NHCH istaucomeri c with where Z is imidazolyl when Y is imidazolyl and Z is ClCH when Y is SCH or C]. W 3 CH o When Y is SCH;, or Cl this reaction iscarried out 1 2 under the conditions given for Process 6. step 1. Exam-N-C-NH-C=N-CH ple 7 below gives the conditions when Z and Y are bothimidazolyl. 3

Nomenclature of the final products R 0 O H H-N=C-N-C-N allophanimidicacid R2 H H Positions:

I N l 2 3 it N 1 2 3 l CH O S O C u I ll IH3 for example:N-C-N=C-N-C--NH-C-CH Y i 3 CH -CH CH CH Name: cyclohexylN-methyl-N-ethylcarbamoyl-2- methyl-4-tert-butylthioallophanimidateName: allyl N-methyl-4.4-dimethylthioallophanimidate lt should be keptin mind that. where R H. tauto- 40 The compounds of this invention canalso exist in meric forms of the molecule are possible and do exist:geometrically isomeric fmms (Ci-5 and trims and 3 5 R x X X R R X x R tiI n l n I 5 4 N-C- N=C-N-C-N N-C-N-C=N-f-C-N /i 2 H 5 2 H 5 F0... (A)Form lfR H. all compounds of this class will still be named until 115 on in structures C and D. as outlined above.

X X R X X 1 1 ,2 l I 1 2 N-C- N=C-NH--R is tautomeric with N-C-NH-C=N--RPositions: I I l 3 2 1 N Compound (A) is a pseudourea derivative;Compound Compound C and D have different physical properties (B) is anallophanimidate. Since the name of Comsuch as infrared spectra.

lORMULA'l'lON ANI) USl-I ()l' llll-i COMPOUNDS 'lhe compounds of formulaI are useful as hcrhicides. 'l'hey may he used at rates of 2.5 to 40kilogram/hcu tare to control all vegetation in industrial sites. alongrights-of way. pipelines. tank farms. and the like. At rates of (H25 toh kilogram/hectare certain of these compounds can he used for selectiveweed control in many crops including asparagus. soybeans. stone fruits.pineapple. sugarcane. sisal. alfalfa. and corn. The precise rate ofmaterial to use in any situation will depend upon the weeds to hecontrolled. climatic and edaphic conditions and whether selective weedcontrol is desired.

The compounds of this invention may be combined with all otherherbicides and are particularly useful in comhination with hromacilt3-sechutyl-5-hromo-omethy luracil diuron (3-/3.4-dichlorophenyl/- l ldimethyl-urea paraquat l.l '-dimethyl--l.-l'- hipyridinium ion). 1.]-dimeth vl-3.3-(N-tert-hutylcarhaunt\yloxyphcnyl )urea. 4-amino-(\-terthutyl-3- lnethyl-thio-as-triazin-5t4H) one. and the S-tria/ines such as2-ehloro--l ethylamino-o-isopropylamiuo-S- tria/ine. for controlling abroad spectrum of weeds.

The compounds of formula I can he formulated for herbicidal use in thevarious ways which are conventional for herbicides ofsimilar physicalproperties. Useful formulations include wettahle powders. oilsuspensions and solutions. aqueous dispersions. dusts. granules.pellets. and high strength compositions. Broadly speaking. theseformulations consist essentially of about I to 90% by weight ofherhicidally active material (including at least one compound of formulaI in a herhicidally effective amount) and at least one of a) ahout (H to20% by weight of surface active agent and h) about 5 to M i by weight ofessentially biologically inert solid or liquid diluent. Morespecifically, the various types of formulations will generally containthese ingredients in the following approximate proportions.

'l'he actual percentages that can he realized with a U particularcompound of formula I will depend upon its physical properties.

The manner of making and using such herbicidal formulations is describedin numerous patents. See. for example. l.uckenhaugh US. Pat. No.3.309.192. Loux US. Pat. No. 3.235.357. 'l'odd U.S. Pat. No. 2.655.445.Hamm et al. US. Pat. No. 2.8o3.752. Scherer et al. US. Pat. No.3.079.244. (iysin et al. U.S. Pat. No. 2.891.855. and Barrons US. Pat.No. 2.642.354.

While conventional application of sprayahle formulations have usuallyheen made in a dilute form (for example at a rate of about 200 litersper hectare or more). the compounds of formula I can also he applied athigher concentrations in the typical ultra-lowvolume" (Ul.\-') or lowvolume applications from aircraft or ground sprayers. For this purpose\vettahle powders can he dispersed in small amounts of aqueous ornonaqueous carrier. The emulsiliahle concentrate suspensions can he useddirectly or with minor dilution. Special compositions. particularlysuitable for Ul.\' applications are solutions or finely dividedsuspensions in one or more carrier such as petroleum oils.dialkylformamides. N-alkylpyrrolidones. and dimethylsulfoxide.

Herhicidal activity of the compounds of this invention was discovered ina greenhouse test. Seeds ofcrabgrass (Digiluriu spp. harnyardgrass(lz'chinmhlou cruxgulli). wild oats (.-lveml /i1!uu). (uxxiu luru.morningglory (lpomeu spp. mustard (Brusxieu spp. marigold ('I'ugelesspp.). dock (Rmma crixpux). and nutsedge ((yperux rommlus) tubers wereplanted in sand or soil and treated preemergence with the chemicalsdissolved in a solvent. At the same time johnsongrass (.S'm'glnunlmlepense) having four leaves. crahgrass and barnyardgrass with threeleaves and nutsedge from tuhers with two leaves were treatedpostemergence. Treatment rates are indicated in the following 'lahle.'lreated plants and controls were maintained in a greenhous for lo days.then all species were compared to controls and lercent By vvt-i m 55visually rated for responses to treatment. A qualitative rating (type ofinjury) was made; the letter was used weuahlt- Ponders 25 no a 7;) l toto indicate chlorosis. and the letter (i to indicate ()ll Suspensions oit. Sulutlons i B 55 u l growth retardation. A quantltatn e ratmg as alsoAqueous [)ispelslulls to so .u) so v m made on a scale of (l to It); arating ol 0 means no ettect l i Q W and a rating of It) means maximumeffect. e.g. com- (uanulesaud l'ellets l ls (n m t) 15 I1 k. R l t. h.hl V I r Sump", p c c l .llll1! .\..lll tns test or some lg y .tctluwalons no m u in o 1 compounds of this invention lollow:

'lahle lostelma'gcnulreemergence l.h. .Iohnllarnllarn- Mornper Nuts son-(rah yard (rah yard Wild Nutsing Mus- Mari- 15 By using the appropriatereactants. the following illustrative compounds of formulae 1. II and Vcan be prepared similarly:

Compounds of Formula V N-methylethylcarhamoyll -methylthioformimidoylchloride N-methylhutylcarhamoyll -methylthioformimidoyl chlorideNdiethylcarhamoyl l -methylthioformimidoyl chloride N-dihutylcarhamoyll-methylthioformimidoyl chloride N-diallylcarhamoyll-methylthioformimidoyl chloride N-pentamethylenecarhamoyll-methylthioformimidoyl chlorideN-diethylenoxycarhamoyll-methylthioformimidoyl chlorideN-methylethylcarhamoyl-l-ethylthioformimidoyl chlorideN-methylbutylcarbamoyll -isopropylthioformimidoyl chlorideN-diethylcarbamoyll -butylthioformimidioyl chloride N-dihutylcarhamoyll-cyclohexylthioformimidoyl chloride N-diallylcarbamoyll-ethylthioformimidoyl chlorideN-pentamethylenecarhamoyll-ethylthioformimidoyl chlorideN-diethylenoxycarbamoyll -propylthioformimidoyl chloride Compounds ofFormula II methyl N-methyl-4 4-diethylenoxythioallophanimidate ethyl4-methyl-4-ethylthioallophanimidate isopropyl4-methyl-4-butylthioallophanimidate butyl 44-diethylthioallophanimidatebenzyl 4.4-dibutylthioallophamimidate sec-butyl4.4-diallylthioallophanimidate ethyl4.4-tetramethylenethioallophanimidate ethyl N-octyl-44-dimethylthioallophanimidate hutylN-sec-hutyl-4-methyl-4-ethylthioallophanimidate ethylN.4-dibutyl-4-methylthioallophanimidate cyclohexylN-isopropyll4.4-diethylthioallophanimi date isopropylN-propyl-4.4-dibutylthioallophanimidate Compounds of Formula 1 methylphanimidate m.p l l2-l 13C methylN-dimethylcarbamoyl-4-ethylthioallophamimidate. m.p. 95-97CN-dimethylcarbamoyl-4-methylthioallo- 6 16 methylN-dimethylcarbamoyl-4-propylthioallophanimidate. m.p. 6674C methylN-dimethylcarhamoyl-4-isopropylthioallophanimidate m.p. 86-89C methylN-dimethylcarbamoyl-4-butylthioallophanimidate 'n,,'-" 1.5530 methylN-dimethylcarbamoyl-4-octylthioallophanimidate. [1 L531! methylN-dimethylcarhamoyl-4-allylthioallophanimidate. m.p. 5558C methylN-dimethylcarbamoyl-4-pr0pynylthioallophanimidate methylN-dimethylcarbamoyl-4-cyclohexylthioallophanimidate. m.p. 889lC methylN-dimethylcarbamoyl-4-cyclohexylmethyltliioallophanimidate methylN-dimethylcarbamoyl-4-norbornylthioallophanimidate methylN-dimethylcarbamoyl-4-phenylthioallophanimidate. m.p. l22-l23C methylN-dimethylcarbamoyl-4-( o-fluo rophenyl )thioallophanimidate. m.pl25l27C methyl N-dimethylcarbamoyl-4-( 3 .4-

dichlorophenyl)thioallophanimidate. m.p. l54l55C methylN-dimethylcarbamoyl-4-( p-methoxyphenyl )thioallophanimidate m.p.l26l27C methyl N-methylethylcarbamoyl'4-tert-butylthioallophanimidatemethyl N-methylbutylcarbamoyl-4-allylthioallophanimidate methylN-diallylcarbamoyl-4-methylthioallophanimidate methylN-dibutylcarbamoyl-4-methylthioallophanimidate methylN-dibutylcarbamoyl-4-phenylthioallophanimidate methylN-dibutylcarbamoyl-4-(3 4-dichlorophenyl)thioallophanimidate methylN-pentamethylenecarbamoyl-4-tert-butylthioallophanimidate ethylN-dimethylcarbamoyl-4 methylthioallophanimidate. m.p. l()9l l 1C ethylN-dimethylcarbamoyl-4-ethylthioallophanimidate isopropyl phanimidatecyclohexyl N-dimethylcarbamoyl-4-isopropylthioallophanimidate isopropylphanimidate allyl N-dimethylcarbamoyl-4-allylthioallophanimidatecyclopentyl N-dimethylcarbamoyl-4-propynylthioallophanimidate isopropylN-dimethylcarbamoyl-4-cyclohexylthioallophanimidate hexylN-dimethylcarbamoyl-4-cyclohexylmethylthioallophenimidate ethylN-dimethylcarbamoyl-4-phenylthioallophanimidate methylN-dimethylcarbamoyl-4-tert-butyll .3-dithioallophanimidateN-dimethylcarbamoyl-4-propylthioallo-N-dimethylcarbamoyl-4-butylthioallomethylN-dihutylcarbamoyl-4-methyl-1.3-dithioallophanimidate methylN-dimethylcarbamoyl-4-cyclohexyl-l.3-dithioallophanimidate methylN-diallylcarbamoyl-4-phenyll 3-dithioallophanimidate methylN-dimethylcarbamoyl-4-( 3 4-dichlorophenyl l,3-dithioallophanimidatemethyl N-dimethylcarbamoyl-2-methyl-4-( 3.4-

dichlorophenyl)-thioallophanimidate. m.p. 87-89C.

methyl N-dimethylcarbamoyl-2methyl-4-phenylthioallophanimidate hylN-dimethylcarbamoyl-2-methyl-4- fluorophenyl)thioallophanimidate m.p.74-77C methyl N-dimethylcarhamoyl-2-methyl--l-(pmethoxyphenyl)thioallophanimidate methyl N-dimethylcarhamoyl-lmethyl-4(pbromophenyl)thioallophanimidate. m.pi 9899C.

methyl N-dimethylcarbamoyl-2-ethyl-4-(pcyanophenyl )thioallophanimidatemethyl N-dimethylcarbamoyl-2-ethyl4-(pcumenyl)thioallophanimidate methylN-dimethylcarbamoyl-2-propyl-44pnitrophenyl )thioallophanimidate methylN-dimethylcarbamoyl-Z-isopropyl-4-(mchlorophenyl )thimtllophanimidatemethyl N-dimethylcarbamoyl-2-sec-butyl-4-( 3 .5-

dichlorophenyl) thioallophanimidate methylN-dimethylcarban1oyl-2-butyl-4-(ptrifluoromethylphenyl)-thioallophanimidate methylN-methylethylcarbamoyl-2-methyl-4-phenylthioallophanimidate methylN-methylbutylcarbamoyl-2-hutyl-4-(ofluorophenyl)thioallophanimidatemethyl cyanophenyl )thioallophanimidate methylN-dibutylcarbamoyl-Z-propyl-4-(p bromophenyl)thioallophanimidate methylN-dibutylcarbamoyl-2-ethyl-4-( mchlorophenyl)thioallophanimidate methylN.N-pentamethyleneearbamoyl-2-methyl-4- phenylthioallophanimidate methylN.N-diethylenoxycarbamoyl-2-methyl-4- phenylthioallophanimidate ethylN-dimethylcarbamoyl-Z-methyl-4phenylthioallophanimidate isopropylN-dimethylcarbamoyl-Z-methyl-44ofluorophenyl)thioallophanimidutecyclohexyl N-dimethylcarbamoyl-2-methyl4-(pmethoxyphenyl)thioallophanimidate ethylN-dimethylcarhamoyl-Z-methyl-4-(pbromophenyl)thioallophanimidate propylN-dimethylcarbamoyl-2-ethyl-4-(pcyanophenyl)thioallophanimidate ethylN-dimethylcarbamoyl-2-ethyl-4-(p-cumenylnhioallophenimidate hexylN-dimethylcarbamoyl-2-propyl-4-(pnitrophenyl)thioallophanimidate propylN-dimethylcarbamoyl-Z-isopropyl-4-( mchlorophenyl)thioallophanimidateethyl N-dimethylcarbamoyl-2-sec-butyl-4-( 3.5-

dichlorophenyl )-thioallophanimidate EXAMPLE 2 To a solution of 65 partsof dimethylcarbamoylisothiocyanate (a compound of formula VI) in 350parts methylene chloride are added within minutes at 0C. parts of cone.aqueous ammonia with good agitation. The resulting slurry of crystals isstirred for an additional I5 minutes at 0C and then filtered to give 70parts of l l-dimethyl-4-thiobiuret (a compound of formula Vll). m.p.l84-l85C.

To a solution of 58.5 parts of l.l-dimethyl-4- thiobiuret in 200 partsof water. 200 parts of methanol N-diethylcarbamoyl-Z-isopropyl-4-(p and32 parts of 50% aqueous sodium hydroxide are added at 25C. within l0minutes 62.5 parts of iodoethanev The reaction mass is then stirred at25C. for 2 hours. Evaporation of the methanol and part of the waterunder vacuum gives 64 parts of crude ethyl 4.4-dimethylthioallophanimidate (a compound of formula ll). which isrecrystallized from water-methanol (50:50) and shows a melting point of9()-93C.

A solution of 5 parts of ethyl 4.4-dimethylthioallophanimidate and L8parts of methylisocyanate in parts of methylene chloride was refluxedfor 2 hours. After evaporation of the solvent. the residue wasrecrystallized from ethylacetate to give ethyl N-dimethylcarbamoyl-4-methylthioallophanimidate (a compound of formula I).m.pi l09l l l.5C.

By using the appropriate reactants. the following illustrative compoundsof formulae I and ll can be prepared similarly:

Compounds of Formula II propyl 4.4-dimethylthioallophanimidate benzyl4.4-dimethylthioallophanimidate ethyl NA,4-trimethylthioallophanimidatebutyl Nethyl-4A-dimethylthioallophanimidate propyl N-propyl-44dimethylthioallophanimidate ethylN-isopropyl-4.4-dimethylthioallophanimidate isopropyl N-butyl-44-dimethylthioallophanimidate propyl 4,4-diethylthioallophanimidateisopropyl 4 4-dipropylthioallophanimidate butyl4.4-dibutylthioallophanimidate benzyl 4-ethyl-4methylthioallophanimidatebutyl N-ethyl-4-isopropyl-4-methylthioallophanimidate propyl N-propyl-44-diisopropylthioallophanimidate ethylN-isopropyl-4.4-diethylthioallophanimidate isopropylN-butyl-4.4-dibutylthioallophanimidate ethyl4.4-dimethylthioallophanimidate isopropyl 44-dimethylthioallophanimidate allyl 4.4-dimethylthioallophanimidatedimethylthioallophanimidate henzyl 4,4-dimethylthioallophanimidatemethyl N-allyl-44-dimethylthioallophanimidate methyl N-propargyl-44-dimethylthioallophanimidate butyl 4.4-

Compounds of Formula 1 N-diethylcarbamoyl-4-tert-butylthioallopropylNdimethylcarbamoyl-4-tert-butylthioallophanimidate. m.p. l02-l0-1Cisopropyl N-dimethylcarbamoyl-4-tert-butylthioallophanimidate. wax

methyl N-dimethylcarbamoyl-Z-allyl-4-(phenyl)thioallophanimidate.

methyl N-dimethylcarbamoyl-2-propynyl-4- (phenyl)thioallophanimidateallyl N-dimethylcarbamoyl-4-tert-butylthioallophanimidate. m.p. 9o--98Cbutyl N-dimethylcarbamoyl-4-tert-hutylthioallophanimidate. m.p. 6466Cbenzyl N-dimethylcarbamoyl-4-tert-butylthioallophanimidate. m.p. l24l26CEXAMPLE 3 To a solution of 130 parts of dimethylcarbamoylisethiocyanate(a compound of formula Vl). in 700 parts of methylene chloride at C areadded within 1 hour I42 parts of chlorine gas. The resulting redsolution is then evaporated under vacuum to crudedimethylcarbamoylformimidoyl dichloride (a compound of formula Vlll) asresidue. which is then puritied by distillation. b.p. 52C/0.4 mm.

A sodium cyclohexylmercaptide solution. prepared from 5.4 parts ofsodium methylate and l 1.6 parts of cyclohexylmercaptan in 100 ml.methanol by refluxing for 10 minutes. is added at l0C. to a solution of16.9 parts of dimethylcarbamoylformimidoyl dichloride in 50 ml methanol.prepared at -l0C. After stirring the reaction mixture for 10 minutes at-l0C. (NaCl pres em). 5 parts of gaseous ammonia are sparged into themixture at l0C. and then the temperature allowed to rise to 30C. Whenthe temperature has fallen back to 25C.. the NaCl is filtered and thefiltrate evaporated. For purification. the product is then dissolved inmethylene chloride and repeatedly extracted with dilute aqueoushydrochloric acid. The HCl-extracts are combined. and after filtrationthrough Celite. the pH is adjusted to 7 by the addition of sodiumhydroxide. After cooling to 0C.. the precipitated solids are isolated byfiltration and are purified by recrystallization from petroleumether togive pure cyclohexyl 4.4-dimethylthioallophanimidate (a compound offormula ll). m.p. 84.586C.

A mixture of 5 parts of cyclohexyl 4.4-dimethylthioallophanimidate and 4parts t-butylisocyanate in 70 parts of methylene chloride is refluxedfor 2 hours. 5

After evaporation of the solvent. the oily residue is triturated withpetroleumether to give solids. which are recrystallized from cyclohexaneto give pure cyclohexyl N-dimethylcarbamoyl-4-t-butylthioallophanimidate(a compound of formula I).

By using the appropriate reactants. the following illustrative compoundsof formulae l and ll can be prepared similarly:

COMPOUNDS OF FORMULA lll allyl N-butyl-4.4-dibutylthioallophanimidatesec-butyl N-isopropyl-4.4-diisopropylthioallophariimidate allyl N-(Z-butynyl)-4.4-dimethylthioallophanimidatecyclooctyl-4.4-dimethylthioallophanimidate2-octenyl-4.4-dimethylthioallophanimidate Compounds of Formula l allylN-dimethylcarbamoyl-4-tert-butylthioallophanimidate allylN-dimethylcarbamoyl-4-methylthioallophanimidate sec-butylN-dimethylcarbamoyl-4-tert-butylthioallophanimidate cyclohexylN-dimethylcarbamoyl-4-tert-butylthioallophanimidatephenyl-N-dimethylcarbamoyl-4-tert-butylthioallophanimidate cyclohexylN-dimethylcarbamoyl-4-allylthioallophanimidate allylN-dimethylcarbamoyl-4-allylthimillophanimidatesec-butyl-N-dimethylcarbamoylA-allylthioallophanimidate allylN-dimethylcarbamoyl-4-cyclohexylthioallophanimidate sec-butylN-dimethylcarbamoyl-4-cyclohexylthioallophanimidate cyclohexylN-dimethylcarbamoyl-4-cyclohexylthioallophanimidate allylN-dimethylcarbamoyl-2-(Z-butynyl)-4-phenylthioallophanimidate sec-butylN-dimethylcarbamoyl-2-isopropyl-4-( 3,4-

dichlorophenyl )-thioallophanimidate cyclohexylN-dimethylcarbamoyl-2-methyl-4-(mchlorophenyl)thioallophanimidatecyclohexyl N-diethylcarbamoyl-4-tert-butylthioallophanimidate phenylN-diethylcarbamoyl-4-tert-butylthioallophanimidate cyclohexylN-dipropylcarbamoyl-4-allylthioallophanimidate allylN-isopropyl-N-methylcarbamoyl-4-allylthioallophanimidate sec-butylN-diethylcarbamoyl-4-allylthioallophanimidate allylN-diethylcarbamoyl-4-cyclohexylthioallophanimidate allylN-diethylcarbamoyl-2-butyl-4-phenylthioallophanimidate sec-butylN-diethylcarbamoyl-2-isopropyl-4-( 3.4-

dichlorophenyl)-thioallophanimidate methylN-dimethylcarbamoyl-4-benzylthioallophanimidate cyclooctylN-dimethy]carbamoyl-4-isopropylthioallophanimidate Z-octenylN-dimethylcarbamoyl-4-isopropylthioallophanimidate EXAMPLE 4 To asolution of l6.9 parts of dimethylcarbamoylformimidoyl dichloride (acompound of formula Vlll) in 25 ml methanol. prepared at -l0C. is addedwithin 10 minutes at l0C. a solution of 5.4 parts sodium methylate in mlmethanol. Sodium chloride precipitates. The reaction mixture is stirredfor l0 minutes at l0C and then 5 parts of gaseous ammonia are spargedinto the mixture at l 0C. The temperature is then allowed to rise to25C. the methanol evaporated under vacuum. and the residue trituratedwith methylene chloride. After filtration of the inorganic salts. themethylene chloride filtrate is evaporated and the residue recrystallizedfrom a little water to give pure methyl 4.4-dimethylallophanimidate (acompound of formula ll). m.p. 80-82.5C.

Parts of methyl 4.4-dimethylallophanimidate and 20 ml oft-hutylisocyanate are refluxed overnight. The next day the solution isevaporated to give an oil. which crystallizes when triturated withpetroleum-ether under cooling. In order to remove some unreactedstarting material and by-products. the solids are first triturated withwater and filtered. After drying the solids are then triturated withcarbon tetrachloride and impurities removed by filtration. The carbontetrachloride filtrate is then evaporated and the residue recrystallizedfrom petroleum-ether to give pure methyl N-dimethylcarhamoyl-4-t-butylallophanimidate (a compound of Formula 1) mp.96-98C.

By using the appropriate reactants. the following illustrative compoundsof formulae l and I] can be prepared similarly:

Compounds of Formula ll ethyl 4.4-dimethylallophanimidate isopropyl4.4-dimethylallophanimidate propyl 4.4-dimethylallophanimidate allyl4,4-dimethylallophanimidate butyl 4.4-dimethylallophanimidate cyclohexyl4,4-dimethylallophanimidate methyl N.4,4-trimethylallophanimidate propylN.4.4-trimethylallophanimidate methylN-butyl-4.4-dimethylallophanimidate ethyl 4.4 diethylallophanimidateisopropyl 4.4-diethylallophanimidate propyl 4.4-dibutylallophanimidateallyl 4.4-diisopropylallophanimidate butyl 4.4-diethylallophanimidatecyclohexyl 4.4-dihutylallophanimidate Compounds of Formula I EXAMPLE 5 2Parts of methyl 4-isopropylallophanimidate (a compound of formula ll)and 5 parts of isopropyl isocyanate are stirred overnight at roomtemperature in 5 parts methylene chloride with a catalytic amount ofdibutyltin dilaurate. The solvent is removed under reduced pressure togive a solid residue which is recrystallized from hexane: chlorobutane(1:1). Parts of pure methylN-isopropylcarbamoyl-4-isopropylallophanimidate (a compound of formulaI). m.p. 8689C. is collected.

Using an appropriate compound of formula ll from the list below and anappropriate isocyanate. each com-N-dimethylcarbamoyl-4-isopropylallophanim i-N-dimethylcarbamoyl-4-tertpound of formula I listed below can beprepared similarlv:

Compounds of Formula ll methyl 4-tert-butylallophanimidate methyl4-cyclohexylallophanimidate methyl 4-cyclooctylallophanimidate methyl,4-octylallophanimidate methyl 4-allylallophanimidate methyl4-eyclopentylallophanimidate methyl 4-cyclopropylallophanimidate methyl4-0yelopropylmethylallophanimidate methyl4-cyclohexylmethylallophanimidate methyl 4-( 2-cyclooetylethyl)allophanimidate methyl 4-( norborn-Z-yl )allophanimidate methyl4-propargylallophanimidate methyl 4-( hut-Z-ynyl )allophanimidate methyl4-methoxyallophanimidate methyl 4-(Z-chloroethyl)allophanimidate methyl4-( l.ll-trichloroethyl)allophanimidate methyl 4-( Z-bromoethyl)allophanimidate methyl 4-(Z-iodoethyl)allophanimidate methyl4-trifluoromethylallophanimidate methyl 4-fluoromethylallophanimidatemethyl 4-( Z-methoxyethyl )allophanimidate methyl4-ethoxymethylallophanimidate methyl 4-methylallophanimidate methyl4-ethylallophanimidate ethyl 4-butylallophanimidate methyl4-benzylallophanimidate methyl 4-( I-ethylthioethyl)allophanimidatemethyl 4-( Z-cyanoethyl )allophanimidate methyl4-methoxycarhonylmethylallophanimidate methyl 4-acetonylallophanimidatemethyl 4-(Z-chlorocyclohexyl)allophanimidate methyl 4-( 3hromocyclohexyl)allophanimidate methyl 4-( Z-methylcyclohexyl )allophanimidate methyl4-( 3.4-dimethylcyclopentyl )allophanimidate methyl4-(4-hutylcyclohexyl)allophanimidate methyl 4-( Z-ethylcyclopropyl)allophanimidate methyl 4-sec-butylallophanimidate methyl4-phenylallophanimidate Compounds of Formula 1 methylN-tert-hutylcarhamoyl-4-terthutylallophanimidate m.p. l2()l22C methylN-cyclohexylcarhamoyl-4-cyclohexylallophanimidate methylN-methylcarbamoyl-4-cyclooctylallophanimidate methylN'octylcarbamoyl-4-ethylallophanimidate methylN-allylcarhamoyl-4-allylallophanimidate. m.p.

methyl N cyclopentylcarbamoyl-4-cyelopentylallophanimidate methylN-cyclopropylcarbamoyl-4-cyclopropylallophanimidate methylN-cyclopropylmethylcarbamoyl-4- cyclopropylmethylallophanimidate methylN'cyclohexylmethylcarhamoyL-icyclohexylmethylallophanimidate methylN-methylcarbamoyl-4-( Z-cyclooetylethyl )allophanimidate methyl N-(norhorn-Z'yl )carhamoyl-4- methylallophanimidate methylN-propargylcarhamoyl-4-propargylallophanimidate methylN-isopropylcarhamoyl-4-( but-Z-ynyl )allophanimidate 23 methylN-isopropylcarbamoyl-4methoxyallophanimidate methyl N-( Z-chloroethyl)carhamoyl-4-( Z-chloroethyl- )allophanimidate methylN-isopropylcarbamoyl-4-( l.2.2-trichloroeth \'l- )allophanimidate methylN-methylcarlmmoyl-4-( Z-bromoethyl )allophanimidate methylN-tert-butylcarhamoyl-4-t 2iodoethyl )allo phanimidate methylN-methylcarbamoyl-4-perfluoropropylallophanimidate methylN-isopropylearbamoyll-trifluoromethylallophanimidate methylN-tert-butylcarhamoyll-fluoromethylallophanimidate methylN-methylcarbamoyl-4-(2-methoxyethyl)allophanimidate methylN-tert-butylcarbamoyl-4-ethoxymethylallophanimidate methylN-cyclohexy|carbamoyl-4-(Z-methylthioethyl- )allophanimidate methylN-ethylcarbamoyl-4-( Z-ethylthioethyl )allophanimidate methylN-(Z-eyanoethyl)carbamoyl-4-(Z-cyanoethyl- )allophanimidate methylN-benzylcarbamoyl-Lisopropylthioallophanimidate methylN-(p-methylbenzylcarbamoyl)-4-methylthioallophanimidate methyl N-(p-chlorobenzylcarbamoyl )-4-tert-hutylthioallophanimidate methylN-tert-butylcarbamoyl-4-methoxycarbonylmethylallophanimidate methylN-methylcarbamoyl-4-acetonylallophanimidate methylN-isopropylcarbamoyl-4-(Z-chlorocyclohexyl- )allophanimidate methylN-propylearbamoyl-4-(3-bromocyclohexyl)allophanimidate methylN-isopropylearbamoyl-4-(Z-methylcyelohexyl- )allophanimidate methylN-tert-butylcarbamoyl-4-( 3 .4-

dimethylcyclopentyl)-allophanimidate methylN-methylcarbamoyl-4-(4-butylcyclohexyl)allomethylN-methylcarbamoyl-4-phenylallophanimidate methylN-tert-butylcarbamoyl-4-secbutylallophanimidate methylN-sec-butylcarbamoyl-4-isopropylallophanimidate. m.p. 6670C methylbutylallophanimidate methyl N-methylcarbamoyl-4-allylallophanimidatemethyl N-allylcarbamoyl-4-tert-butylallophanimidateN-methylcarbamoyl4-tertethyl N-butylcarbamoyl-4-allylallophanimidateethyl N-butylcarbamoyl-4-tert-butylallophanimidate ethylN-butylcarbamoyl-4-cyclohexylallophanimidate ethyl N-butylcarbamoyl-4-(p-bromophenyl )allophanimidate methyl N-ethylthiocarbamoyl-4-tertbutylallophanimidate methyl phenylallophanimidateN-ethylthiocarbamoyl-4- EXAMPLE 6 methyl 4-methylthioallophanimidatemethyl 4-tert-butylthioallophanimidate methyl 4-ethylthioallophanimidatemethyl 4-octylthioallophanimidate methyl 4-isopropylthioallophanimidatemethyl 4-allylthioallophanimidate methyl 4-butylthioallophanimidatemethyl 4( l-cyclooctylethyl)thioallophanimidate methyl 4-( norborn-Z-yl)thioallophanimidate methyl 4-propargylthioallophanimidate methyl4-(hex-3-ynyl)thioallophanimidate methyl 4-propylthioallophanimidatemethyl 4-methoxythioallophanimidate methyl 4( Z-chloroethyl)thioallophanimidate methyl 4-( l.2.2-trichloroethyl)thioallophanimidatemethyl 4-( Z-bromoethyl )thioallophanimidate methyl4-(2-iodoethyl)thioallophanimidate methyl4-perfluoropropylthioallophanimidate methyl4-trifluoromethylthioallophanimidate methyl4-fluoromethylthioallophanimidate methyl4-(Z-methoxyethyl)thioallophanimidate methyl4-(ethoxymethylthioallophanimidate methyl 4-(2-methylthi0ethyl)thioallophanimidate methyl 4-( Z-ethylthioethyl)thioallophanimidate methyl 4-( Z-cyanoethyl)thioallophanimidate methyl4-methoxycarbonylmethylthioallophanimidate methyl4-acetylthioallophanimidate methyl4-(Z-chlorocyclohexyl)thioallophanimidate methyl 4-( 3-bromocyclohexyl)thioallophanimidate methyl 4-( Z-methylcyclohexyl)thioallophanimidatemethyl 4-( 3.4-dimethylcyclopentyl )thioallophanimidate methyl4-(4-butylcyclohexyl)thioallophanimidate methyl 4-( Z-ethylcyclopropyl)thioallophanimidate methyl 4-sec-butylthioallophanimidate methyl4-cyclohexylthioallophanimidate methyl 4-phenylthioallophanimidate butyl4-methylthioallophanimidate butyl 4-allylthioallophanimidate octyl4-butylthioallophanimidate ethyl 4-tert-butyll .3-dithioallophanimidatemethyl 4-allyl-l .3-dithioallophanimidate methyl 4-isopropyll.3-dithioallophanimidate methyl 4-tert-hutyll .3-dithioallophanimidatemethyl 4-see-butyl-l.B-dithioallophanimidate Compounds of Formula Imethyl N-methylcarhamoyl-4-tert-hutylthioallophanimidate. m.p. l32l33Cmethyl N-tert-hutylcarbamoyl-4-cyclohexylthioallophanimidate map. l37-l44C methyl Nethylearbamoyl-4-allylthioallophanimidate methylN-oetylcarhamoyl-4-methylthioallophanimidate methylN-oetylearbamoyl--l-propynylthioallophanimidate methylN-isopropylearhamoyl-4-cyelohexylmethylthioallophanimidate. mp. l23l 25Cmethyl N-allylearhamoyl-4-phenylthioallophanimidate methylN-ethylearhamoyl-4-( 3,4-dichlorophenyl )thioallophanimidate methylN-butylcarbamoyl-4-(peyanophenyl)thioallophanimidate methylN-see-butylearbamoyll-isopropylthimtllophanimidate. mp. l()4l l 1Cmethyl N-methylearhamoyl--l-( Z-eyclooetylethyl )thioallophanimidatemethyl NmethylcarhamoyL-l-( norhorn-Z-yl )thioallophanimidate methylN-propargylcarbamoyI-4-propargylthioallophanimitlate methyl Nisopropylearbamoyl-4-(4- ethyleyelohexyl )thioallophanimidate methylN-isopropylearhamoyl-4-methoxythioallophanimidate methyl N-(Z-chloroethyl )carbamoyl-4-( 2- ehloroethyl )thioallophanimidate methylN-isopropylearbamoyl-4-( l .11.]-

triehloroethyl )thioallophanimidate methyl Nmethylcarbamoyl-4-(Z-bromoethyl)thioallophanimidate methylN-tert-butylcarbamoyl-4-( Z-iodoethyl)thioallophanimidate methylN-methylcarbamoyl-4-perfluoropropylthioallophanimidate methylN-isopropylcarbamoyl-4-trifluoromethylthioallophanimidate methylN-tert-hutylcarhamoyl-4-fluoromethylthioall0- phanimidate 5 methylN'methylearbamoyl-4-(Z-methoxyethyl)thloallophanimidate methylN-tert-butylcarhamoyl-4-ethoxymethylthioallophanimidate methylN-cyclohexylcarbamoyl-4-( Z-methylthioethyl thioallophanimidate methylN-ethylcarbamoyl-4-(Z-ethylthioethyl)thioallophanimidate methyl N-(Z-eyanoethyl )Carhamoyl-4-l 2- cyanoethyl )thioallophanimidate methylN-tert-butylcarhamoyl-4- methoxyearbonylmethylthioallophanimidate methylN-methylcarbamoyl--l(eyelooet-Z-enyl)thioallophanimidate methylN-isopropylcarbamoyl-4-l 2- chlorocyclohexyl )thioallophanimidate methylN-propylcarhamoyl-4-t 3.4.4-

trichlorocyclohexyl)thioallophanimidate butylN-methylearbamoyl-4-methylthioallophanimidate butylN-allylearbamoyl-4-tert-butylthioallophanimidate hutylN-methylearbamoyl-4-(m-ehlorophenyl)thioallophanimidate octylN-butylcarhamoyl-4-allylthioallophanimidate octylNbutylcarbamoyl-4-tert-hutylthioallophanimidate octylN-butylcarhamoyl-4-p-nitrophenyl )thioallophanimidate ethylN-tert-hutylthioearbamoyl-4-isopropylthioallophanimidate methylN-allylthiocarhamoyl 4-tert-butylthioallophanimidate methylN-isopropylthioearhamoyl-4-methylthioallophanimidate methyl Nisopropylthiocarbam0yl-4-isopropylthioallophanimidate methylN-tert-hutylthiocarbamoyl-4-tert-butylthioallophanimidate methylN-sec-butylthiocarbamoyl-4-sec-butylthioallophanimidate methylN-methylearbam0yl-4-(cyclopent-Z-enyl)thioallophanimidate EXAMPLE 7methyl N-methylcarbamoyl 4-(hexahydro-4.7methanoindenyl)thioallophanimidate methyl N-methylcarbamoyl-4-(3,4-dibromophenyl )thioallophanimidate methyl N-methylcarbamoyl-4-(p-tolyl )thioallophanimidate methylN-ethylcarhamoyl-4-(a.a-dimethylhenzyl)thioallophanimidate methylN-methylearhamoyl-4-furfurylthioallophanimidate methylN-isopropylcarhamoyl-4-(hut-Z-enyl)thioallo' phanimidate 17.5 Partsmethyl 4-isopropylthioallophanimidate (a compound offormula II) isdissolved in 150 parts methylenechloride. This solution is addeddropwise to a stirred solution of l7.8 g N.N'-thiocarbonyldiimidazole inI50 parts methylene chloride. The temperature is maintained at duringthe addition and for 18 hours thereafter. Still maintaining 0. 9.3 partsaniline is added. After this addition the mixture is allowed to warm toroom temperature for 2 hours. The reaction mixture is then washed withseveral portions of water. to remove the imidazole formed. dried withmagnesium sulfate. and the solvent evaporated at room temperature underreduced pressure. The residue is a good grade ofcrude methylN-isopropylcarbamoyl-4-phenyll.3-dithioallophanimidate (a compound offormula I).

By substituting the appropriate methyl 4-substitutedthioallophanimidates for the methyl 4-isopropylthioallophanimidateand/or appropriate amine for the aniline. the following allophanimidatescan be prepared similarly:

methyl N-tetramethylenecarbamoyl-4-phenyll .3-

dithioallophanimidate methyl N-tert-butylcarbamoyl-4-phenyll.3-dithioallophanimidate methyl N-sec-butylcarbamoyl-4-phenyl-l.3-dithioallophanimidate methylN-diisopropylcarbamoyl-4-phenyl-1.3-dithioallophanimida'te methylN-isopropylcarbamoyl-4-cyclohexyl-1.3-dithioallophanimidate methylN-ethylthiocarbamoyl-4-tert-butyll .3-dithioallophanimidate methylN-tert-butylthiocarbamoyl-4-phenyl-l.3-dithioallophanimidate methylN-cyclopropylcarbamoyl-4-phenyl l .3-dithioallophanimidate methylN-isopropylthiocarbamoyl4-isopropyl-l .3-

dithioallophanimidate methyl N-tert-butylthiocarbamoyl-4-tert-butyll .3-

dithioallophanimidate methyl N-tert-butylthiocarbamoyl-4-isopropyll .3-

dithioallophanimidate EXAMPLE 8 319 Parts of 2-methyl-Z-thiopseudoureasulfate (salt of a compound of formula lX). 2300 parts of acetonitrileand 400 parts triethylamine are combined. 400 Parts isopropylisocyanateare added rapidly and the temperature comes to 35C. The solvent isremoved under reduced pressure 2 days later and the oil is dissolved indichloromethane and washed with water. The organic layer is dried andevaporated to give a tan solid. The solid is recrystallized fromdichloromethanezhexane to give 813 parts methyl N-isopropylcarbamoyl-4-isopropylthioallophanimidate (a compound of formula I). (m.p. l25-l27C).

The corresponding isomer can be formed as follows: 25 Parts of thegeometrical isomer of methylN-isopropylcarbamoyl-4-isopropylthioallophanimidate is dissolved in 25parts dimethylformamide and heated to 40C. After l hour. 12 parts ofwater is added to give 21 parts white solid after drying (m.p.l25-l27C.). The infrared spectrum is different from starting material.

By substituting different isocyanates for the isopropyl isocyanate inthe above example. the following compounds of formula I are prepared:methyl N-tert-butylcarbamoyl-4-tert-butylthioallophanimidate. mp. ll53Cmethyl N-cyclohexylcarbamoyl-4-cyclohexylthioallophanimidate. m.p.l38-l40C methyl N-allylcarbamoyl-4-allylthioallophanimidate methylN-cyclopentylcarbamoyl-4-cyclopentylthioallophanimidate methylN-cyclopropylcarbamoyl-4-cyclopropylthioallophanimidate methylN-cyclopropylmethylcarbamoyl-4- cyelopropylmethylthioallophanimidatemethyl N-eyclohexylmethylcarbamoyl-4-cyclohexylmethylthioallophanimidate methylN-sec-butylcarbamoyl-4-sec-butylthioallophanimidate. m.p. 105 l 08CEXAMPLE 9 To a solution of I19 parts of 4-thiobiuret (a compound offormula X) in 400 parts of water. 400 parts of methanol and 80 parts of50% aqueous sodium hydroxide are added within it) minutes at C. I42parts 15 of iodomethane. The reaction mass is then stirred at 25C for 2hours. Evaporation of the methanol and part of the water under vacuumgives crude methyl thioallophanimidate (a compound of formula ll). whichcan be used without further purification for subsequent reactions.

A mixture of 13 parts of methyl thioallophanimidate 74 parts ofmethylene chloride and 6 parts of methylisocyanate is refluxed for 2hours. After standing overnight at room temperature. the solution isevaporated under vacuum to give crude methyl N-carbamoyl-4-methylthioallophanimidate (a compound of formula I).

By using the appropriate reactants. the following additionalillustrative compounds of formula I and ll can be prepared similarly:

Compounds of Formula ll ethyl thioallophanimidate isopropylthioallophanimidate propyl thioallophanimidate butyl thioallophanimidateoctyl thioallophanimidate Compounds of Formula I methylN-carbamoyl-4-ethylthioallophanimidate methylN-carbamoyl-4-isopropylthioallophanimidate methylN-carbamoyl-4-tert-butylthioallophanimidate ethylN-carbamoyl-4-cyclohexylthioallophanimidate isopropylN-carbamoyl-4-allylthioallophanimidate propylN-carbamoyl-4-allylthioallophanimidate butylN-carbamoyl-4-tert-butylthioallophanimidate octylN-carbamoyl-4-methylthioallophanimidate octylN-carbamoyl-4-phenylthioallophanimidate octyl N-carbamoyl-4-( 3.4-dichlorophenyl )thioallophanimidate EXAMPLE l0 5.4 Parts ofdimethylcarbamoyl chloride is combined with I0 parts pyridine andstirred until the temperature returns to 25C. 8.0 Parts methyl4.4-dimethylthioallophanimidate (a compound of formula ll). in partsmethylene chloride is added in one portion. The mixture is refluxedovernight. then cooled to give a white solid. The solid is removed andthe organic layer is extracted with 200 parts water at pH 3. dried andevaporated to give 5 parts methyl N-dimethylcarbamoyl-4.4-dimethylthioallophanimidate (a compound of formula I). m.p. ll5.5-ll7.5C.

By substituting dimethylthiocarbamoyl chloride for the dimethylcarbamoylchloride and methyl 4.4- dimethyl-l .3-dithioallophanimidate for themethyl 4.4- dimethylthioallophanimidate. there can be obtained methylN-dimethylthiocarbamoyl-4.4-dimethyll .3-dithioallophanimidate.

By using the appropriate compound of formula [I from the list below. thecompounds of formula I in the list below can be prepared similarly:

Compounds of Formula ll methyl 4.4diethylthioallophanimidate methyl4.4-tetramethylenethioallophanimidate methyl4.4-hexamethylenethioallophanimidate methyl4.4-ethylenethioallophanimidate methyl4.4-ethyleneoxyethylenethioallophanimidate methyl4-isopropylA-methylthioallophanimidate methyl4-butyl-4-methylthioallophanimidate methyl4-cthyl-4-methylthioallophanimidate methyl4-tertbutyl-4-methylthioallophanimidate methyl4.4-dimethylallophanimidate methyl 4.4-diethylallophanimidate methyl4-isopropyl-4-methylallophanimidate methyl4-tert-butyl-4-methylallophanimidate methyl4.4-tetramethyleneallophanimidate ethyl 4.4-dimethylthioallophanimidateisopropyl 44-dimethylthioallophanimidate tert-butyl4.4-dimethylthioallophanimidate benzyl 4.4-dimethylthioallophanimidatemethyl 4.4-dimethyl l .3-dithioallophanimidate methyl 4-phenyl4-methyll.3-dithioallophanimidate methyl4.4-pentamethylene-l3-dithioallophanimidate Compounds of Formula Imethyl N-dimethylcarbamoyl-4.4-diethylthioallophanimidate methylN-dimethylcarbamoyl--l.4-tetramethylenethioallophanimidate methylN-dimethylcarbamoyl-4.4-hexamethylenethioallophanimidate methylN-dimethylcarbamoyl-4.-l-ethylenethioallophanimidate methylN-dimethylcarbamoyl-4.4-

ethyleneoxyethylenethioallophanimidate methylN-dimethylcarbamoyl-4-isopropyl4-methylthioallophanimidate methylN-dimethylcarbamoyl-4-butyl-4-methylthioallophanimidate methylN-dimethylcarbamoyl--l-ethyl-4-methylthioallophanimidate methylN-dimethylcarbamoyl-4-tert-butyl-4-methylthioallophanimidate methylN-dimethylcarbamoyl-4 4-dimethylallophanimidate methylN-dimethylcarbamoyl-4.4-diethylallophanimidate methylN-dimethylcarbamoyl-4-isopropyl-4- methylallophanimidate methylN-dimethylcarbamoyl-4-tert-butyl-4- methylallophanimidate methylN-dimethylcarbamoyl-4.4-tetramethyleneallophanimidate ethylN-dimethylcarbamoyl-4.4-dimethylthioallophanimidate isopropylN-dimethylcarbamoyl-4.4-dimethylthioallophanimidate tert-butylN-dimethylcarbamoyl-4.4dimethylthioallophanimidate benzylN-dimethylcarbamoyl-4.4-dimethylthioallophanimidate methylN-dimethylcarbamoyl-4.4-dimethyl l .3-dithioallophanimidate methylN-dimethylthiocarbamoyl-4.-l-dimethylthioallophanimidate methylN-dimethylthiocarbamoyl-4.4-

pentamethylenedithimillophanimidate EXAMPLE I l 5.6 Parts ofZ-methyl-2-thiopsuedourea sulfate (salt of a compound of formula IX). isplaced in 50 parts water and cooled to 5C. 4.5 Parts of methylchlorothioformate is added in one portion followed by 4.8 parts of 50%sodium hydroxide added dropwise. A solid forms and is collected after 30minutes. The N-( lamino- 1 -methylthiomethylene )thiolmethylcarbamate (acompound of formula Xll). m.pv -65C. is dissolved in 40 parts ofmethylene chloride with 4.2 parts of tert-butylisocyanate and stirredovernight. The solvent is removed under reduced pressure to give asolid. This solid is recrystallized from chlorobutanezhexane lzl to give6.2 parts of methyl 4-tert-butyl-N-methylthiolcarbonyl-l-thioallophanimidate (a compound of formula III)m.p. lO5-l06C.

7.9 Parts of methyl4-tert-butyl-Nmethylthi0lcarbonyl-l-thioallophanimidate and 2.9 parts ofmorpholine are combined in 50 ml of methanol and stirred overnight. Thesolution is poured into 50 parts water and the resulting solid iscollected. The solid is recrystallized from acetonitrile to give 2.4parts of methyl N-tert-butylcarbamoyl-44-ethyleneoxyethylenethioallophanimidate (acompound of formula I). m.p. l43-l44C.

By using the appropriate reactants. the following illustrative compoundsof formulae l and Ill can be prepared sililarly:

Compounds of Formula II] methyl4-isopropyl-N-methylthiolcarbonyl-l-thioallophanimidate methyl4-methyl-N-methylthiolcarbonyl-l-thioallophanimidate methyl4-sec-butyl-N-methylthiolcarbonyl-l-thioallophanimidate methyl4-phenyl-N-methylthiolcarbonyll thioallophanimidate methyl4-benzyl-N-methylthiolcarbonyll -thioallophanimidate methyl4-ethyl-N-methylthiolcarbonyll -thioallophanimidate methyl4isopropyl-N-methylthiolcarbonyll .3-dithioallophanimidate methyl4-methyl-N-methylthiolcarbonyll .3-dithioallophanimidate methyl4-phenyl-N-methylthiolcarbonyl-1.3-dithioallophanimidate methyl4-tert-butyl-N-methylthiolcarbonyl-l.3-dithioallophanimidate Compoundsof Formula I methyl N-isopropylcarbamoyl-4.4-dimethylthioallophanimidatemethyl N-ethylcarbamoyl-4,4-tetramethylenethioallophanimidate. m.p.l0ll05C methyl N-methylcarbamoyl-4.4-pentamethylenethioallophanimidatemethyl N-phenylcarbamoyl-4,4-bis( 2-chloroethyl )thioallophanimidate 31methyl N-benzylcarbamoyl-4.4-dipropylthioallophanimidate methylNtert-butylcarbamoyl-4.4-tetramethylenethioallophanimidate. m.p.l48-l5()C methyl N-isopropylcarbamoyl-4.4-diethylthioallophanimidate.m.p. 67-68C methyl N-isopropylthiocarbamoyl-4.4-dimethylthioallophanimidate methyl N-isopropylthiocarbamoyl-4.4-

tetramethylenethioallophanimidate methylN-phenylthiocarbamoyl-4.4-dipropylthioallophanimidate methylN-tert-butylthiocarbamoyl-4.4-

tetramethylenethimillophanimidate EXAMPLE 12 18.8 Parts of methyl4-butyl-4-methylthioallophanimidate (a compound of formula ll) isdissolved in 200 parts methylene chloride with parts triethylamine. l 1Parts methyl chlorothioformate is added slowly dropwise and a solidforms. After 2 hours the solid is collected and the filtrate isevaporated to give methyl 4-butyl-4-methyl-N-methylthiolcarbonyl-l-thioallophanimidate (a compound of formula III).This product is dissolved in 50 parts methanol and 10.] partsdiisopropylamine is added in one portion. The mixture is stirredovernight. then poured into 50 parts water to give a solid. The solid iscollected and recrystallized from acetonitrile to give a good yield ofmethyl N-butyl-N- methylcarbamoyl-4.4-diisopropylthioallophanimidate (acompound of formula I).

By using the appropriate compound of formula ll and the appropriateamine. the following compounds of formula I can be prepared similarly:methyl N-tetramethylenecarbamoyl-4.4-dimethylthioallophanimidate methylN-tetramethylenecarbamoyl-4.4-dibutylthioallophanimidate methylN-tetramethylenecarbamoyl-4-isopropyl-4- methylthioallophanimidatemethyl N-tetramethylenecarbamoyl-4.4-pentamethyleneallophanimidatemethyl N-tetramethylenecarbamoyl-4.4-bis( 2- chloroethyl)-thioallophanimidate methylN-tetramethyleneearbamoyl-4.4-diisopropylthioallophanimidate methylN-tetramethylenecarbamoyl-4.4-diethylthioallophanimidate EXAMPLE 13 5.0Parts of methyl N-tert-butylcarbamoyl-4.4- dimethylthioallophanimidate(a compound of formula I) is suspended in water and 1.5 parts 50% sodiumhydroxide is added with stirring. After solution is obtained. the wateris removed under reduced pressure to give methylN-tert-butylcarbamoyl-4.4-dimethylthioallophanimidate. sodium salt.

By substituting the appropriate compounds of formula l and bases. thefollowing salts can be prepared in similar manner: methylN-isopropylcarbamoyl-4-isopropylthioallophanimidate. potassium saltmethyl N-tert-butylcarbamoyl-4-isopropylthioallophanimidate. calciumsalt methyl N-methylcarbamoyl-4-isopropylthioallophamimidate. magnesiumsalt methyl N-tert-butylcarbamoyl-4-tert-butylthioallophanimidate.thioallophanimidate. lithium salt methylN-tert-butylcarbamoyl-4-tert-butylthioallophanimidate. ammonium salt 7methyl N-tert-butylcarbamoyl-4-tert-butylthioallophanimidate. cesiumsalt EXAMPLE I4 A solution of 12.5 parts thiophosgene in 150 partsmethylene chloride is prepared. This is cooled to. and maintained at.-l()C while a mixture of methyl 4.4- diethylthioallophanimidate (acompound of formula II) 18.9 parts. triethylamine 10 parts. andmethylene chloride 150 parts. is added over a hour period. After theaddition is complete the mixture is stirred at l()C for an additionalhour. lsopropylamine. 12 parts. is added and the mixture is allowed towarm to room temperature and stirred 1 hour. The reaction mixture isthen washed with an equal volume of ice water and the methylene chloridelayer collected. dried with magnesium sulfate. and the solventevaporated at room temperature under vacuum. The residue is a good gradeof crude methyl N.N-diethylcarbamoyl-4-isopropyl-l.3-dithioallophanimidate.

I claim:

1. A method for the control of undesired vegetation comprising applyingto the locus of such undesired vegetation a herbicidally effectiveamount of a compound of the formula:

wherein:

R,. R R and R are each independently selected from the group consistingof hydrogen; alkyl of 1 through 8 carbon atoms: alkenyl of 3 through 4carbon atoms; cycloalkyl of 3 through 8 carbon atoms; cycloalkenyl of 5through 8 carbon atoms: cycloalkylalkyl of4 through 10 carbon atoms;bicycloalkyl of7 through 10 carbon atoms; hydrocarbyl arylalkyl of 5through 9 carbon atoms; alkynyl of 3 through 4 carbon atoms; and phenyl:

R is hydrogen: alkyl of I through 4 carbon atoms; alkynyl of 3 through 4carbon atoms: or alkenyl of 3 through 4 carbon atoms;

R is alkyl of 1 through 8 carbon atoms; cycloalkyl of 5 through 8 carbonatoms: alkenyl of 3 through 8 carbon atoms: phenyl; or benzyl: and

X,. X and X are each independently selected from oxygen and sulfur;

provided that:

a. at least one of R,. R R and R,-, is other than hydrogen:

b. no more than one of R,. R R and R is phenyl or arylalkyl;

c. the total number of carbon atoms in R, and R does not exceed 10:

d. the total number of carbon atoms in R and R does not exceed 10; and

e. when R is normal alkyl of 3 through 8 carbon atoms. cycloalkyl of 6through 8 carbon atoms and benzyl. and R is hydrogen. and one of R,. R R

1 x R x3 Rs II II N-C-N=CN-C-N l .32 Xz-Il6 4 wherein:

R R R and R are each independently selected from the group consisting ofhydrogen: alkyl of 1 through 8 carbon atoms; alkenyl of 3 through 4carbon atoms; cycloalkyl of 3 through 8 carbon atoms; cycloalkenyl of 5through 8 carbon atoms: cycloalkylalkyl of4 through carbon atoms;bicycloalkyl of 7 through 10 carbon atoms: hydrocarbyl arylalkyl of 5through 9 carbon atoms: alkynyl of 10 provided that:

3 through 4 carbon atoms; and phenyl:

R is hydrogen; alkyl of I through 4 carbon atoms; alkynyl of 3 through 4carbon atoms: or alkenyl of 3 through 4 carbon atoms:

R is alkyl of I through 8 carbon atoms; cycloalkyl of 5 through 8 carbonatoms: alkenyl of 3 through 8 carbon atoms; phenyl; or benzyl; and

X.. X,. and X,, are each independently selected from oxygen and sulfur;

a. at least one of R,. R R and R is other than hydrogen:

b. no more than one of R,. R R and R is phenyl or arylalkyl:

c. the total number of carbon atoms in R and R does not exceed l0;

d. the total number of carbon atoms in R.. and R does not exceed 10: and

e. when R. is normal alkyl of 3 through 8 carbon atoms. cycloalkyl of 6through 8 carbon atoms and benzyl. and R is hydrogen. and one of R R Rand R,-, is phenyl. then only one of the other R,. R R and R,-, can beother than hydrogen: and the alkali metal. alkaline earth and ammoniumsalts of the above compounds in which R is hydrogen.

4. Composition as defined in claim 3 wherein the compound is methylN-isopr0pylcarbamoyl-4- isopropylthioallophanimidate.

1. A method for the control of undesired vegetation comprising applyingto the locus of such undesired vegetation a herbicidally effectiveamount of a compound of the formula:
 1. A METHOD FOR THE CONTROL OFUNDESIRED VEGETATION COM- 1 PRISING APPLYING TO THE LOCUS OF SUCHUNDESIRED VEGETATION A HERBICIDALLY EFFECTIVE AMOUNT OF A COMPOUND OFTHE FORMULA: R1-N(-R2)-C(=X1)-N=C(-X2-R6)-N(-R3)-C(=X3)-N(-R4)-R5WHEREIN: R1, R2, R4, AND R5 ARE EACH INDEPENDENTLY SELECTED FROM THEGROUP CONSISTING OF HYDROGEN, ALKYL OF 1 THROUGH 8 CARBON ATOMS; ALKENYLOF 3 THROUGH 4 CARBON ATOMS; CYCLOALKYL OF 3 THROUGH 8 CARBON ATOMS;CYCLOALKENYL OF 5 THROUGH 8 CARBON ATOMS; CYCLOALKYLALKYL OF 4 THROUGH10 CARBON ATOMS; BICYCLOALKYL OF 7 THROUGH 10 CARBON ATOMS; HYDROCARBYLARYLALKYL OR 5 THROUGH 9 CARBON ATOMS; ALKYNYL OF 3 THROUGH 4 CARBONATOMS; AND PHENYL; R3 IS HYDROGEN; ALKYL OF 1 THROUGH 4 CARBON ATOMS;ALKYNYL OF 3 THROUGH 4 CARBON ATOMS; OR ALKENYL OR 3 THROUGH 4 CARBONATOMS; R6 IS ALKYL OF 1 THROUGH 8 CARBON ATOMS; CYCLOALKYL OF 5 THROUGH8 CARBON ATOMS; ALKENYL OF 3 THROUGH 8 CARBON ATOMS; PEHNYL; OR BENZYL;AND X1, X2, AND X3 ARE EACH INDEPENDENTLY SELECTED FROM OXYGEN ANDSULFUR; PROVIDED THAT: A. AT LEAST ONE OF R1, R2, R4, AND R5 IS OTHERTHAN HYDROGEN; B. NO MORE THAN ONE OF R1, R2, R4, AND R5 IS PHENYL ORARYLALKYL; C. THE TOTAL NUMBER OF CARBON ATOMS IN R4 AND R2 DOES NOTEXCEED 10; D. THE TOTAL NUMBER OF CARBON ATOMS IN R4 AND R5 DOES NOTEXCEED 10; AND E. WHEN R6 IS NORMAL ALKYL OF 3 THROUGH 8 CARBON ATOMS,CYCLOALKYL OF 6 THROUGH 8 CARBON ATOMS AND BENZYL, AND R3 IS HYDROEN,AND ONE OF R1, R2, R4, AND R5 IS PHENYL, THEN ONLY ONE OF THE OTHER R1,R2, R4, AND R5 CAN BE OTHER THAN HYDROGEN; AND THE ALKALI METAL,ALKALINE EARTH AND AMMONIUM SALTS OF THE ABOVE COMPOUNDS IN WHICH R3 ISHYDROGEN.
 2. Method as defined in claim 1 wherein the compound is methylN-isopropylcarbamoyl-4-isopropylthioallophanimidate.
 3. A compositionfor the control of undesirable vegetation comprising at least one of (a)a surface active agent and (b) a biologically inert solid or liquiddiluent and a herbicidally effective amount of a compound of theformula: